Insecticidal diaminoguanidine hydrazone compounds

ABSTRACT

The invention is insecticidal diaminoguanidine hydrazone compounds which are also effective antifeeding agents for insects and methods for their preparation.

This application is a division of copending application Ser. No. 788,296, filed Oct. 17, 1985, in issue, which is a division of U.S. Pat. No. 4,649,148, issued on Mar. 11, 1986.

The invention is diaminoguanidine hydrazone compounds of the formula (I) ##STR1## wherein R₁ ' and R₂ ' are H, and R₁ and R₂ are individually selected from fluoro, chloro, bromo, trifluoromethyl, CF₃ CH₂ O, CHF₂ X, CF₃ X, CHY₂ --CF₂ X, or CHFYCF₂ X, where X is O or S and Y is F or Cl; or R₁ and R₁ ' or R₂ and R₂ ' are --OCF₂ O--, --OCF₂ CHFO--, --OC(CH₃)₂ --O-- or --OCF₂ CF₂ O--;

R is H, ##STR2## where R₃ is C₁ -C₂ alkyl, or C₁ -C₂ haloalkyl, R₄ is hydrogen or C₁ -C₂ alkyl; or R₃ and R₄ when taken together may form a ring represented by CH₂ (CH₂)_(n) -- where n is 3 or 4; R₅ is C₁ -C₄ alkyl optionally substituted with one to three halogens or C₃ -C₄ alkenyl, with the proviso that when R is ##STR3## R₁ and R₂ are CF₃ CH₂ O, CHF₂ X, CF₃ X, CHY₂ CF₂ X, or CHFYCF₂ S, where X is O or S and Y is F or Cl; R₁ and R₁ ' or R₂ and R₂ ' are --OCF₂ O--, --OC(CH₃)₂ --O--, --OCF₂ CHFO or --OCF₂ CF₂ O--.

While the use of diaminoguanidine compounds as antiprotozoal agents and especially as anticoccidial agents is known in the art as described in U.S. Pat. No. 3,992,446 and Belgian Pat. No. 824,811, there is no suggestion in the literature that diaminoguanidine hydrazone compounds are effective insecticidal agents or further that some of these compounds exhibit antifeeding activity when applied to plants.

The diaminoguanidine hydrazone compounds of the invention as well as other diaminoguanidine hydrazone compounds are effective in controlling lepidopterous insects and are useful for protecting agronomic crops, trees, shrubs, and ornamentals from attack by these insects. Many of these compounds also exhibit antifeeding activity thus providing additional protection to treated plants.

Novel formula (Ia) diaminoguanidine dialkyl ureas of the invention wherein R is ##STR4## in formula (I) may be readily prepared by the reaction of an appropriately substituted diaminoguanidine of formula (Ib) wherein R is H in formula (I) with from 1 to 2 molar equivalents of N,N-disubstituted carbamoyl chlorides of formula (III) in a solvent such as acetonitrile in the presence of a tertiary amine such as triethylamine or diisopropylethylamine as illustrated in Flow Diagram I below. ##STR5## wherein R₁, R₁ ', R₂, R₂ ', R₃ and R₄ are as described above.

Formula (Ia) diaminoguanidine monosubstituted ureas may be prepared by the reaction of the appropriately substituted formula (Ib) diaminoguanidine with from 1 to 1.5 molar equivalents of a formula (IV) isocyanate in an inert solvent such as ether as illustrated in Flow Diagram II below. ##STR6## wherein R₁, R₁ ', R₂, R₂ ' and R₄ are as described above.

When R₁ and R₂ and R₁, R₁ ' and R₂, R₂ ' are not the same, both of the above reaction sequences give rise to isomeric mixtures of the formula (Ia) products as indicated below. ##STR7## wherein R₁, R₁ ', R₂, R₂ ', R₃, and R₄ are as described above.

Diaminoguanidine hydrazones of formula (Ib) may be prepared by the reaction of two molar equivalents of an appropriately substituted aldehyde of formula (Va) dissolved in an organic solvent with an alcoholic or aqueous alcoholic solution of a diaminoguanidine salt of the formula ##STR8## as illustrated in Flow Diagram III(a) below.

Uniquely, unsymetrical diaminoguanidines where R₁ ≠R₂ and R₁, R₁ '≠R₂, R₂ ' may then be obtained cleanly by the novel reaction of a symetrical diaminoguanidine with a minimum of one molar equivalent of hydroxylamine hydrochloride followed by reaction of the thus-formed monosubstituted guanidine with an appropriately substituted aldehyde of formula (Vb) as illustrated in Flow Diagram III(b) below. ##STR9##

The Formula (Ib) insecticidal diaminoguanidines may also be converted to insecticidal Formula (Ic) diaminoguanidines by reaction of with 1.0 to 1.25 molar equivalents of an appropriately substituted chloroformate of formula (VI) in an organic solvent such as acetonitrile, ether, toluene, methylene chloride and the like, in the presence of a tertiary amine such as triethylamine or diisopropylethylamine as illustrated in Flow Diagram (IV) below. ##STR10## wherein R₁, R₁ ', R₂, R₂ ' and R₅ are as described above.

The present invention is further illustrated by the following non-limiting examples.

EXAMPLE 1 Preparation of p-(2,2,2-trifluoroethoxy)benzaldehyde ##STR11##

Potassium hydroxide pellets (85%, 13.2 g, 0.2 mol) are added to 4-hydroxybenzaldehyde (24.4 g, 0.2 mol) and 18-crown-6 (2.6 g, 5% mol) in diglyme (150 mL). The red reaction mixture is stirred for 16 hours at room temperature and then a solution of 2,2,2-trifluoroethyl-p-toluenesulfonate (50.8 g, 0.2 mol) in diglyme (100 mL) is added over 30 minutes, after which the mixture is allowed to stir at room temperature for 45 minutes. The resulting suspension is then heated at reflux for 24 hours. The mixture is cooled to 10° C. and poured into ice water (1300 mL). The organic materials are extracted with ether (4×200 mL), and the extracts washed with 5% sodium hydroxide (2×100 mL), water (2×100 mL) and saturated sodium chloride (1×100 mL), and dried over MgSO₄. Evaporation of the ether gives an amber oil which is purified by high performance liquid chromatography using silica gel on a Waters 500 unit and 50:50 hexane and methylene chloride as eluant to give 12.3 g of the title product with R_(f) 0.25. Anal. Calcd for C₉ H₇ F₃ O₂ (204.15) C, 52.94; H, 3.43. Found C, 52.04; H, 3.59.

EXAMPLE 2 Preparation of 1,3-bis{[p-(tetrafluoroethoxy)benzylidene]-amino}guanidine ##STR12##

A solution of p-tetrafluoroethoxybenzaldehyde (35.07 g, 0.158 mol) in 2B alcohol (20 mL) is added over 70 minutes to a stirred slurry of diaminoguanidine hydrochloride (9.91 g, 0.079 mol) in 2B alcohol (60 mL) and water (15 mL) at 45° C. The resulting solution is refluxed for one hour, cooled to 5° C. and the hydrochloride salt collected by filtration and washed with cold alcohol and ether to give a white solid (40.5 g, 2 crops, 95%):mp 262°-264° C.

The hydrochloride salt (40.53 g, 0.076 mol) is stirred with ethyl acetate (250 mL) and neutralized with aqueous potassium carbonate (3.62 mol, 50 mL). The organic layer is washed with water, dried over Na₂ SO₄, filtered and evaporated to a yellow solid. Crystallization from benzene-hexane gives the product as a yellow powder (37.4 g, 99%) with mp 125°-130° C.

EXAMPLE 3 Preparation of 1-amino-3-{[p-(trifluoromethyl)benzylidene]amino}-guanidine, hydrochloride and p-tolualdehyde,α,α,α,-trifluoro-, oxime, (E)- ##STR13##

A mixture of 1,3-bis{[p-(trifluoromethyl)benzylidene]amino}guanidine (15.0 g, 0.0374 mol), hydroxylamine hydrochloride (2.76 g, 0.0393 mol) and ethanol (95%, 100 mL) is refluxed for one hour and 30 minutes. After stirring at room temperature for 16 hours, the reaction mixture is cooled in a freezer and the white solid is filtered (7.25 g). The filtrate is evaporated to approximately 30 mL and then cooled. The resulting purple solid (4.4 g) is collected by filtration and reslurried in hot chloroform (75 ml). Filtration gave the title hydrochloride as a white solid with mp 246°-249° C. (dec).

The filtrate is evaporated to approximately 10 mL and then cooled. The title oxime is collected by filtration as a white powder (1.72 g) mp 98°-102.5° C.

Using a similar procedure, 1-amino-3-p{[p-(1,1,2,2-tetrafluoroethoxy)benzylidene]amino}guanidine hydrochloride (white solid, mp 205°-212° C.); 1-amino-3-{p-(trifluoroethoxy)benzylidene]amino}guanidine hydrochloride (white powder; mp 235°-238° C.); and 1-amino-3-(p-chlorobenzylideneamino)guanidine hydrochloride may be prepared. The second products of the reactions, p-(1,1,2,2-tetrafluoroethoxy)benzaldehyde oxime (pinkish white solid, mp 47°-53.5° C.); α,α,α-trifluoro-p-anilaldehyde oxime (off-white solid, mp 46°-49.5° C.) and p-chlorbenzaldehyde oxime may also be isolated from the reactions.

EXAMPLE 4 Preparation of 1-{[p-(1,1,2,2-tetrafluoroethoxy)benzylidene]amino}-3-{[p-(trifluoromethyl)benzylidene]amino}guanidine ##STR14##

p-Tetrafluoroethoxybenzaldehyde (1.7 g) in 4 mL of ethanol is added over three minutes to a stirred and warm mixture of 2.0 g of 1-amino-3-{[p-(trifluoromethyl)benzylidene]amino}guanidine hydrochloride in 9 mL of 8:1 ethanol/water. After heating at reflux for one hour, the mixture is concentrated in vacuo to give 3.6 g of a white solid. The solids are dissolved in 150 mL of chloroform and treated with 10 mL of 3.6M potassium carbonate and 50 mL of water containing 5% sodium hydroxide. The product is extracted into ethyl acetate 300 mL and the organic layer washed with salt solution, dried over sodium sulfate and concentrated in vacuo to give 3.3 g of yellow solid. Crystallization from hexanechloroform afforded 2.6 g of the title product as a yellow solid with mp 132°-137° C.

Utilizing the procedures of Examples 2 and 4 and substituting the appropriate aldehyde and guanidine yields compounds illustrated below. ##STR15## wherein unless specified R₁ ' and R₂ ' are H.

    ______________________________________                                         Symmetrical diaminoguanidine hydrazones                                                    Free base  Physical                                                R.sub.1 = R.sub.2                                                                          or Salt    appearance  mp °C.                               ______________________________________                                         4-CF.sub.3  Free base  Yellow solid                                                                               181-182                                     4-F         Free base  Pale yellow 166-167                                                            solid                                                   4-F         HCl salt   White solid 289.5-290                                   4-HCF.sub.2 CF.sub.2 O                                                                     Free base  Pale yellow   127-130.5                                                        powder                                                  4-CF.sub.3 O                                                                               Free base  Yellow solid                                                                               118-120                                     4-HCF.sub.2 O                                                                              Free base  Yellow solid                                                                               132-135                                     4-HCF.sub.2 O                                                                              HCl salt   White solid   235-235.5                                 4-HCCl.sub.2 CF.sub.2 O                                                                    Free base  Yellow solid                                                                                 90-92.5                                   4-HCCl.sub.2 CF.sub.2 O                                                                    HCl salt   White solid 243-245                                      ##STR16##  Free base  Yellow solid                                                                               86-91                                        ##STR17##  HCl salt   White solid 241-247                                     4-HCF.sub.2 CF.sub.2 S                                                                     Free base  Yellow solid                                                                               135-139                                     4-HCF.sub.2 CF.sub.2 S                                                                     HCl salt   Yellow white                                                                               273-278                                                            fluffy solid                                                                               (dec)                                       4-CF.sub.3 CH.sub.2 O                                                                      Free base  Light yellow                                                                               160-162                                                            powder                                                  4-CF.sub.3 CH.sub.2 O                                                                      HCl salt   Beige crystal-                                                                             230-236                                                            line solid                                              4-HCF.sub.2 S                                                                              Free base  Yellow solid                                                                               141.5-143                                   4-HCF.sub.2 S                                                                              HCl Salt   White solid 253-254                                                                        (dec)                                       R.sub.1 R.sub.1 '/R.sub.2 R.sub.2 '                                             ##STR18##  HCl salt   White powder                                                                               243-247                                      ##STR19##  HCl salt   White powder                                                                               301-305                                      ##STR20##  Free base  Pale yellow solid                                                                          132-135                                      ##STR21##  HCl salt   White solid 216-244                                     ______________________________________                                          ##STR22##                                                                     Unsymmetrical diaminoguanidine hydrazones                                                       Free base Physical                                            R.sub.1                                                                              R.sub.2    or Salt   appearance                                                                               mp °C.                             ______________________________________                                         CF.sub.3                                                                             Cl         Free base Yellow solid                                                                             184-186                                   CF.sub.3                                                                             Br         Free base Yellow solid                                                                             187.5-188                                 CF.sub.3                                                                             Br         HI salt   Yellow solid                                                                             243-244                                   CF.sub.3                                                                             HCF.sub.2 CF.sub.2 O                                                                      Free base Yellow powder                                                                            132-137                                   Br    HCF.sub.2 CF.sub.2 O                                                                      Free base Yellow powder                                                                            149-158                                   Cl    HCF.sub.2 CF.sub.2 O                                                                      Free base Yellow solid                                                                             177-180                                   Cl    HCF.sub.2 CF.sub.2 O                                                                      HCl salt  White solid                                                                              251-259                                   CF.sub.3 O                                                                           HCF.sub.2 CF.sub.2 O                                                                      Free base Yellow powder                                                                            106-109                                   CF.sub.3 O                                                                           HCF.sub.2 CF.sub.2 O                                                                      HCl salt  White solid                                                                                261-263.5                                                                    (dec)                                     ______________________________________                                    

EXAMPLE 5 Preparation of 4,4-dimethyl-2-{[p-(1,1,2,2-tetrafluoroethoxy)benzylidene]amino}-allophanimidic acid [p-(1,1,2,2-tetrafluoroethoxy)benzylidene]hydrazide ##STR23##

A solution of 1,3-bis{[p-(1,1,2,2-tetrafluoroethoxy)benzylidene]amino}guanidine (29.84 g, 0.06 mol), diisopropylethylamine, (15.51 g, 0.12 mol) and dimethylcarbamoyl chloride (129.2 g, 0.12 mol) in acetonitrile (200 mL) is stirred at reflux for 22 hours. The reaction mixture is cooled, and the acetonitrile is evaporated under reduced pressure. The residue is dissolved in ethyl acetate (250 mL), and the organic solution is washed with water, saturated NaCl and dried over Na₂ SO₄. The solvent is evaporated under reduced pressure, and the residue is crystallized from benzene-hexanes to give the desired product as a yellow solid, mp 141.5°-143.5° C. in 92.9% yield.

Utilizing the above procedure and substituting the appropriate dialkylcarbamoyl chloride and diaminoguanidine hydrazone compound, yields the compounds illustrated below.

    ______________________________________                                          ##STR24##                                                                     R.sub.3   R.sub.4    R.sub.3   R.sub.4                                                                             mp °C.                              ______________________________________                                         CF.sub.3  CF.sub.3   CH.sub.3  CH.sub.3                                                                            124-126                                    Cl        Cl         CH.sub.3  CH.sub.3                                                                            169-161                                    Br        Br         CH.sub.3  CH.sub.3                                                                            172-178                                    CF.sub.3 O                                                                               CF.sub.3 O CH.sub.3  CH.sub.3                                                                            113-115                                    HCF.sub.2 O                                                                              HCF.sub.2 O                                                                               CH.sub.3  CH.sub.3                                                                            83.5-85.5                                  HCCl.sub.2 CF.sub.2 O                                                                    HCCl.sub.2 CF.sub.2 O                                                                     CH.sub.3  CH.sub.3                                                                            153-154                                    HCFClCF.sub.2 O                                                                          HCFClCF.sub.2 O                                                                           CH.sub.3  CH.sub.3                                                                            142-144                                    HCF.sub.2 CF.sub.2 S                                                                     HCF.sub.2 CF.sub.2 S                                                                      CH.sub.3  CH.sub.3                                                                            143-146                                    F         F          CH.sub.3  CH.sub.3                                                                            186-187                                    HCF.sub.2 S                                                                              HCF.sub.2 S                                                                               CH.sub.3  CH.sub.3                                                                            130-133                                    {HCF.sub.2 CF.sub.2 O                                                                    {Br and    CH.sub.3  CH.sub.3                                                                            60-65                                      and Br}   HCF.sub.2 CF.sub.2 O}                                                                     --        --                                              {CF.sub.3 and Br}                                                                        {Br and CF.sub.3 }                                                                        CH.sub.3  CH.sub.3                                                                            129-130                                                         --        --                                              {CF.sub.3 and Cl}                                                                        {Cl and CF.sub.3 }                                                                        CH.sub.3  CH.sub.3                                                                            149-151                                    {CF.sub.3 O and                                                                          {HCF.sub.2 CF.sub.2 O                                                                     CH.sub.3  CH.sub.3                                                                            102-120                                    HCF.sub.2 CF.sub.2 O}                                                                    and CF.sub.3 O}                                                                           --        --                                              CF.sub.3  CF.sub.3   C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                     150-151                                    HCF.sub.2 CF.sub.2 O                                                                     HCF.sub.2 CF.sub.2 O                                                                      C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                      99-100                                    CF.sub.3 O                                                                               CF.sub.3 O C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                     67-70                                      CF.sub.3  CF.sub.3   (CH.sub.2).sub.4                                                                            120-123                                      HCF.sub.2 CF.sub.2 O                                                                     HCF.sub.2 CF.sub.2 O                                                                      (CH.sub.2).sub.4                                                                            136-137                                      ______________________________________                                    

EXAMPLE 6 Preparation of allophanimidic acid, 4-(2-chloroethyl)-2-{[p-(trifluoromethyl)benzylidene]amino}-allophanimidic acid [p-(trifluoromethyl)benzylidene]hydrazide ##STR25##

A solution of 2-chloroethylisocyanate (2.9 g, 0.0275 mol) in ether (8 mL) is slowly added to a slightly turbid mixture of 1,3-bis{[p-(trifluoromethyl)benzylidene]amino}guanidine (10.03 g, 0.025 mol) in ether (200 mL). After stirring for two hours at room temperature, the product is collected by filtration, washed with ether, and dried in a vacuum oven at 50°-60° C. to give 11.78 g of the above product with a mp 133° C.

Utilizing the above procedure and substituting the appropriate substituted or unsubstituted isocyanate and diaminoguanidine hydrazone compound yields the compounds illustrated below.

    ______________________________________                                          ##STR26##                                                                     R.sub.1   R.sub.2     R.sub.3    mp °C.                                 ______________________________________                                         CF.sub.3  CF.sub.3    CH.sub.3   146.5-147                                     Cl        Cl          CH.sub.3   Decomposes                                                                     on heating                                    HCF.sub.2 O                                                                              HCF.sub.2 O CH.sub.3   113.0-114                                     HCF.sub.2 CF.sub.2 O                                                                     HCF.sub.2 CF.sub.2 O                                                                       CH.sub.3   139.5-142.5                                   CF.sub.3  CF.sub.3    C.sub.2 H.sub.5                                                                           180                                           HCF.sub.2 CF.sub.2 O                                                                     HCF.sub.2 CF.sub.2 O                                                                       C.sub.2 H.sub.5                                                                           119.0-120.5                                   HCF.sub.2 CF.sub.2 O                                                                     HCF.sub.2 CF.sub.2 O                                                                       ClCH.sub.2 CH.sub.2                                                                       116.0-118                                     ______________________________________                                    

EXAMPLE 7 Preparation of 3-[p-(trifluoromethyl)benzylidene]-2-{{[p-(trifluoromethyl)benzylidene]amino}amidino}carbazate ##STR27##

Ethyl chloroformate (2.98 g, 0.0275 mol) is added dropwise to a refluxing solution of 1,3-bis{[p-trifluoromethyl)benzylidene]amino}guanidine (10.03 g, 0.025 mol) and diisopropylethylamine "DIPEA" (3.55 g, 0.0275 mol) in acetonitrile (130 mL). After refluxing for one hour the mixture is cooled and acetonitrile (50 mL) is added. The resulting white solids collected by filtration, are washed with acetonitrile and dried in a vacuum oven at 50°-60° C. to give 6.9 g. The solid is slurried in hot isopropanol and filtered to give the product as white fluffy needles (6.0 g), mp 202° C.

EXAMPLE 8 Preparation of 2,2,2-trichloroethyl 3-[p-(trifluoromethyl)benzylidene]-2-{{[p-trifluoromethyl)benzylidene]-amino}amidino}carbazate ##STR28##

A solution of 2,2,2-trichloroethyl chlorformate (2.33 g, 0.011 mol) in ether (10 mL) is added dropwise to a solution of 1,3-bis{[p-(trifluoromethyl)benzylidene]amino}guanidine (4.01 g, 0.01 mol) and triethylamine (1.13 g, 0.011 mol) in ether (80 mL). The resulting mixture is stirred for one hour and then allowed to stand overnight. Additional 2,2,2-trichloroethyl chlorformate (2.33 g, 0.011 mol) and triethylamine 11.13 g, 0.011 mol) are added and stirring continued for four hours. The reaction mixture is filtered and the filtrate evaporated to dryness. The residue is dissolved in ethyl acetate, and the mixture is washed with water, dried over Na₂ SO₄, filtered, and evaporated to a pale yellow solid. Successive crystallizations from toluene and isopropanol gave the title product (0.54 g) with mp 150.5°-151° C.

EXAMPLE 9 Preparation of 3-[p-(trifluoromethyl)benzylidene]-2-{{[p-(trifluoromethyl)benzylidene]amino}amidino}carbazate ester ##STR29##

A solution of 2-chloroethyl chloroformate (235.9 g, 1.65 mol) in acetonitrile (250 mL) is added in a steady stream to a solution of 1,3-bis-{[p-(trifluoromethyl)benzylidene]amino}guanidine (602.0 g, 1.5 mol) and diisopropylethylamine (213.3 g, 1.65 mol) in acetonitrile (7500 mL) while the temperature is maintained below 35° C. Additional acetonitrile (1000 mL) is added and the reaction mixture stirred for one hour. The fluffy white solids are collected by filtration, washed with acetonitrile (2000 mL) and dried to give 610 g of the product with mp 188° C.

Utilizing the procedures of examples 7, 8, and 9 and substituting the appropriate hydrazone and chloroformate gives the compounds illustrated below. ##STR30## wherein unless specified R₁ ' and R₂ ' are H.

    __________________________________________________________________________                              Physical                                              R.sub.1                                                                               R.sub.2                                                                               R.sub.5    appearance                                                                             mp °C.                                 __________________________________________________________________________     CF.sub.3                                                                              CF.sub.3                                                                              CH.sub.3   White solid                                                                            174-174.5                                     HCF.sub.2 CF.sub.2 O                                                                  HCF.sub.2 CF.sub.2 O                                                                  CH.sub.3   White solid                                                                            181-183                                       Cl     Cl     CH.sub.3   White solid                                                                            189.5-190                                     CF.sub.3                                                                              CF.sub.3                                                                              C.sub.2 H.sub.5                                                                           White needles                                                                          202                                           Cl     Cl     C.sub.2 H.sub.5                                                                           White solid                                                                            154-185                                       HCF.sub.2 O                                                                           HCF.sub.2 O                                                                           C.sub.2 H.sub.5                                                                           Pale yellow                                                                            154-155                                                                solid                                                 HCF.sub.2 CF.sub.2 O                                                                  HCF.sub.2 CF.sub.2 O                                                                  C.sub.2 H.sub.5                                                                           White solid                                                                            152.5-155                                     CF.sub.3 O                                                                            CF.sub.3 O                                                                            C.sub.2 H.sub.5                                                                           Cream color                                                                            169-170                                                                solid                                                 CF.sub.3 and Cl                                                                       Br and CF.sub.3                                                                       C.sub.2 H.sub.5                                                                           White solid                                                                            189-189.5                                     HCF.sub.2 S                                                                           HCF.sub.2 S                                                                           C.sub.2 H.sub.5                                                                           Pale yellow                                                                            152-153                                                                solid                                                 HCF.sub.2 O                                                                           HCF.sub.2 O                                                                           C.sub.2 H.sub.5                                                                           Pale yellow                                                                            134-135                                                                solid                                                 CF.sub.3                                                                              CF.sub.3                                                                               -n-C.sub.3 H.sub.7                                                                       White solid                                                                            181-182                                       CF.sub.3                                                                              CF.sub.3                                                                               .sub.-i-C.sub.3 H.sub.7                                                                  White solid                                                                            178-178.5                                     HCF.sub.2 CF.sub.2 O                                                                  HCF.sub.2 CF.sub.2 O                                                                   .sub.-i-C.sub.3 H.sub.7                                                                  White solid                                                                            129-131.5                                     HCCl.sub.2 CF.sub.2 O                                                                 HCCl.sub.2 CF.sub.2 O                                                                  .sub.-i-C.sub.3 H.sub.7                                                                  White solid                                                                            131-133                                       CF.sub.3 O                                                                            CF.sub.3 O                                                                             .sub.-i-C.sub.3 H.sub.7                                                                  White solid                                                                            142-144                                        ##STR31##                                                                             ##STR32##                                                                             -i-C.sub.3 H.sub.7                                                                       White powder                                                                           127.5-130                                     HCF.sub.2 CF.sub.2 S                                                                  HCF.sub.2 CF.sub.2 S                                                                   .sub.-i-C.sub.3 H.sub.7                                                                  Pale yellow                                                                            120-124                                                                fluffy solid                                          CF.sub.3                                                                              CF.sub.3                                                                               -n-C.sub.4 H.sub.9                                                                       White needles                                                                          185                                           CF.sub.3                                                                              CF.sub.3                                                                               .sub.-i-C.sub.4 H.sub.9                                                                  White solid                                                                            184-184.5                                     CF.sub.3                                                                              CF.sub.3                                                                               ##STR33## White solid                                                                            153.5-154                                     CF.sub.3 O                                                                            CF.sub.3 O                                                                             ##STR34## White solid                                                                            126-128.5                                     Cl     Cl                                                                                     ##STR35## White solid                                                                            149-150                                       CF.sub.3                                                                              CF.sub.3                                                                              CH.sub.2 CH.sub.2 Cl                                                                      White solid                                                                            188                                           CF.sub.3 O                                                                            CF.sub.3 O                                                                            CH.sub.2 CH.sub.2 Cl                                                                      Fluffy white                                                                           166-167                                                                solid                                                 HCF.sub.2 CF.sub.2 O                                                                  HCF.sub.2 CF.sub.2 O                                                                  CH.sub.2 CH.sub.2 Cl                                                                      Pale orange-                                                                           128-135                                                                white solid,                                                                   and remelt at                                                                          170-182                                       {HCF.sub.2 CF.sub.2 O                                                                 {Cl and                                                                               CH.sub.2 CH.sub.2 Cl                                                                      Light brown-                                                                           117-119                                       and Cl}                                                                               HCF.sub.2 CF.sub.2 O}                                                    ##STR36##                                                                             ##STR37##                                                                            CH.sub.2 CH.sub.2 Cl                                                                      Off-white powder                                                                       110-137                                       {HCF.sub.3 CF.sub.2 O                                                                 {CF.sub.3 O                                                                           CH.sub.2 CH.sub.2 Cl                                                                      Off-white                                                                              120-180                                       and    and               powder                                                CF.sub.3 O}                                                                           HCF.sub.2 CF.sub.2 O}                                                   HCF.sub. 2 S                                                                          HCF.sub.2 S                                                                           CH.sub.2 CH.sub.2 Cl                                                                      White solid                                                                            138-139                                       CF.sub.3                                                                              CF.sub.3                                                                              CH.sub.2 CH.sub.2 Cl                                                                      Light beige                                                                            155-160                                                                powder                                                CF.sub.3                                                                              CF.sub.3                                                                              CH.sub.2 CH.sub.2 Br                                                                      White solid                                                                            184-185                                       CF.sub.3                                                                              CF.sub.3                                                                              CH.sub.2 CCl.sub.3                                                                        Pale yellow                                                                            150.5-151                                                              solid                                                 CF.sub.3 O                                                                            CF.sub.3 O                                                                            CH.sub.2 CCl.sub.3                                                                        Cream color                                                                            137.5-140                                                              solid                                                 CF.sub.3                                                                              CF.sub.3                                                                              C(CH.sub.3).sub.2CCl.sub.3                                                                Fluffy white                                                                           162-164                                                                solid                                                 CF.sub.3                                                                              CF.sub.3                                                                              CH.sub.2CHCH.sub.2                                                                        White solid                                                                            190                                           HCCl.sub.2 CF.sub.2 O                                                                 HCCl.sub.2 CF.sub.2 O                                                                 CH.sub.2CH White solid                                                                            165-166                                       CF.sub.3 O                                                                            CF.sub.3 O                                                                            CH.sub.2CH.sub.2 CH.sub.2                                                                 White solid                                                                            176.5-177                                     CF.sub.3                                                                              CF.sub.3                                                                               ##STR38## White solid                                                                            146.5-147.5                                   CF.sub.3                                                                              CF.sub.3                                                                              oleyl      White solid                                                                            137-140                                       CF.sub.3                                                                              CF.sub.3                                                                               ##STR39## White solid                                                                            168-169                                       R.sub. 1 R.sub.1 '/R.sub.2 R.sub.2 '                                            ##STR40##     .sub.-i-C.sub.3 H.sub.7                                                                 White solid                                                                            125-132                                        __________________________________________________________________________

EXAMPLE 10

The insecticidal activity of the compounds of this invention is demonstrated by the following tests wherein compounds are evaluated against test insect species at rates of from 10 to 1000 ppm. Test formulations and procedures used for evaluation are as follows:

Test Formulations

A. 100 mg of the test material is weighed, placed in a funnel over a 113 g narrowmouth bottle, rinsed into the bottle with a 35 mL scoop of acetone, followed by a 35 mL scoop of water and another 35 mL scoop of acetone to yield 1000 ppm in 65% acetone. If the material is not soluble, it is broken up with a glass rod and used as a suspension.

B. This stock solution ("A") is used to make 300 ppm solutions or suspensions by pipetting 30 mL of "A" into a bottle containing 70 mL of 50% acetone to yield 300 ppm. Further dilutions in 50% acetone are made as required.

C. Tests requiring 10 ppm acetone solutions: 1 mL of "A" is pipetted into 99 mL of acetone to yield 10 ppm. Additional dilutions are made using 50% acetone as required.

Initial Tests

Tobacco Budworm-Heliothis virescens (Fabricus).

A cotton plant with two true leaves expanded is dipped for three seconds with agitation in 300 ppm solution. A 1.27 to 1.91 cm square of cheesecloth with about 50 to 100 budworm eggs 0-24 hours old is also dipped in the test solution and placed on a leaf of the cotton plant, all being placed in the hood to dry. The leaf with the treated budworm eggs is removed from the plant and placed in a 226 g Dixie cup with a wet 5 cm piece of dental wick and covered with a lid. The other leaf is placed in a similar cup with a wick and a piece of cheesecloth infested with 50-100 newly hatched larvae is added before covering the cup with a lid. After three days at 80° F., 50% relative humidity, observations of egg hatch are made, as well as kill of newly hatched larvae, any inhibition of feeding, or interference of any sort with normal development.

Southern Armyworm-Spodoptera eridania (Cramer).

A Sieva lima bean plant with just the primary leaves expanded to 1.91 cm is dipped for three seconds with agitation in the "A" solution of 1000 ppm and set in the hood to dry. Following this, one leaf is placed in a 9 cm petri dish which has a moist filter paper in the bottom and 10 third-instar armyworm larvae about 1 cm long. This dish is covered and held at 80° F., and 50% r.h. After two days, mortality counts and estimates of the amount of feeding are made. Compounds showing partial kill and/or inhibition of feeding are held for an extra day for further observations. Those materials which produce greater than 75% mortality, or which show only trace feeding damage are further tested.

All compounds showing activity as defined above are retested, using the second leaf on the bean plant, after an interval of seven days from original treatment, as an assay of residual activity.

Secondary Tests

Tobacco Budworm-Heliothis virescens (Fabricus)

Third Instar

Three cotton plants with just expanded cotyledons are dipped in 1000 ppm solution and placed in the hood to dry. When dry, each cotyledon is cut in half, and 10 are each placed in a 28 g plastic medicine cup containing a 1.25 cm dental wick saturated with water, and one third-instar budworm larva is added. The cup is capped and held for three days at 80° F., 50% relative humidity, after which mortality counts are made. Compounds killing more than 75% of the larvae are further tested.

    ______________________________________                                         Rating System                                                                  ______________________________________                                                 0   No effect                                                                  1   11-25%                                                                     2   26-35%                                                                     3   36-45%                                                                     4   46-55%                                                                     5   56-65%                                                                     6   66-75%                                                                     7   76-85%                                                                     8   86-99%                                                                     9   100%                                                               ______________________________________                                    

Data obtained are reported in Table IA, IB and IC below.

    TABLE IA       Evaluation of Diaminoguanidine Hydrazone Urea Compounds as Insecticides       ##STR41##        Mortality Rating  Southern Tobacco Budworm LC.sub.50 /ppm *FD.sub.50      /ppm LC.sub.50 /ppm *FD.sub.50 /ppm Compound Armyworm 1st Instar 3rd      Instar Southern Southern Tobacco Tobacco R.sub.1 R.sub.2 R.sub.3 R.sub.4 1      000 100 10 300 100 10 1000 100 10 Armyworm Armyworm Budworm Budworm        CF.sub.3 CF.sub.3 CH.sub.3 CH.sub.3 9 9 8 8 6 0 9 9 0 15 12  96  3      HCF.sub.2 CF.sub.2 O HCF.sub.2 CF.sub.2 O CH.sub.3 CH.sub.3 9 9 0 9 5 --      8 2  7, 7 8, 6 491 2, 5 Cl Cl CH.sub.3 CH.sub.3 9 0 -- 0 -- -- 0 0 -- --      -- -- -- Br Br CH.sub.3 CH.sub.3 9 9 0 0 -- -- 2 0 -- -- -- -- --      CF.sub.3 O CF.sub.3 O CH.sub.3 CH.sub.3 9 9 9 -- -- -- 9 3 -- 10, 23  8,      30 77, 72 1, 4 HCF.sub.2 O HCF.sub.2 O CH.sub.3 CH.sub.3 9 9 0 0 -- -- 0      -- -- 75 46 -- -- HCCl.sub.2 CF.sub.2 O HCCl.sub.2 CF.sub.2 O CH.sub.3      CH.sub.3 9 9 -- -- -- -- 0 2 -- 26 28 140 <30       ##STR42##       ##STR43##       CH.sub.3 CH.sub.3 9 9 9 -- -- -- 9 4 0 -- -- 201 10  HCF.sub.2 CF.sub.2      S HCF.sub.2 CF.sub.2 S CH.sub.3 CH.sub.3 9 9 3 -- -- -- 6 6 0 -- -- --      -- F F CH.sub.3 CH.sub.3 8 0 -- -- -- -- 0 -- -- -- -- -- -- HCF.sub.2 S      HCF.sub.2 S CH.sub.3 CH.sub.3 9 9 0 -- -- -- 0 -- -- -- -- -- --      HCF.sub.2 CF.sub.2 O and Br and CH.sub.3 CH.sub.3 9 9 9 -- -- -- 6 0 --      -- -- -- -- BR HCF.sub.2 CF.sub.2 O CF.sub.3 and Br and CH.sub.3      CH.sub.3 0 9 0 -- -- -- 6 0 -- -- -- -- -- Br CF.sub.3 CF.sub.3 and Cl      and CH.sub.3 CH.sub.3 9 9 5 -- -- -- 0 0 -- -- -- -- -- Cl CF.sub.3      CF.sub.3 O and HCF.sub.2 CF.sub.2 O and CH.sub.3 CH.sub.3 9 9 -- -- --      -- 7 3 -- -- -- -- -- HCF.sub.2 CF.sub.2 O CF.sub.3 O CF.sub.3 CF.sub.3      CH.sub.3 H 9 9 1 8 0 -- 6 -- -- 5 5 -- -- HCF.sub.2 O HCF.sub.2 O      CH.sub.3 H 9 0 -- 7 -- -- 0 -- -- -- -- -- -- HCF.sub.2 CF.sub.2 O      HCF.sub.2 CF.sub.2 O CH.sub.3 H 9 9 0 -- -- -- 4 -- -- 16, 34 12, 19 --      -- CF.sub.3 CF.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 9 9 7 0 -- -- 4 --      --  8, 12  8, 11 -- -- HCF.sub.2 CF.sub.2 O HCF.sub.2 CF.sub.2 O C.sub.2      H.sub.5 C.sub.2 H.sub.5 9 9 1 -- -- -- 5 0 0 -- -- -- -- CF.sub.3 O      CF.sub.3 O C.sub.2 H.sub.5 C.sub.2 H.sub.5 9 9 0 -- -- -- 8 -- -- -- --      -- -- CF.sub.3 CF.sub.3 C.sub.2 H.sub.5 H 9 0 -- 0 -- -- 0 -- -- -- --      -- -- HCF.sub.2 CF.sub.2 O HCF.sub.2 CF.sub.2 O C.sub.2 H.sub.5 H 9 9 0      -- -- -- 4 -- -- 34 12 -- -- CF.sub.3 CF.sub.3 (CH.sub.2).sub.4 9 9 9 --      -- -- 9 4 0 18, 14 14, 12 1000  30 HCF.sub.2 CF.sub.2 O HCF.sub.2      CF.sub.2 O (CH.sub.2).sub.4 9 9 -- -- -- -- 3 0 -- -- -- -- -- CF.sub. 3 C      F.sub.3 ClCH.sub.2 CH.sub.2 H 9 9 -- 0 -- -- 9 4 -- 11, 37 10, 12 654 13      HCF.sub.2 CF.sub.2 O HCF.sub.2 CF.sub.2 O ClCH.sub.2 CH.sub.2 H 9 8 0 --      -- -- 6 0 0 21 17 -- --      FD.sub.50 = The concentration of insecticide required to reduce insect      feeding by 50%.

                                      TABLE IB                                     __________________________________________________________________________             4                                                                      Diaminoguanidine hydrazones as insecticides                                     ##STR44##                                                                     wherein unless specified R.sub.1 ' and R.sub.2 ' are H                                        Mortality Rating                                                          Free            Tobacco Budworm                                      Compound  Base, B                                                                             Southern Armyworm                                                                         1st Instar                                                                             3rd Instar                                   R.sub.1                                                                           R.sub.2                                                                               or salt, S                                                                          1000                                                                               100 10 300                                                                               100                                                                               10                                                                               1000                                                                              100                                                                               10                                     __________________________________________________________________________     CF.sub.3  B    9   9   0  6  0  --                                                                               8  0  --                                                            9                                                       F         B     9/R*                                                                              2   -- 0  0  --                                                                               3  -- --                                     F         S    9   2   -- -- -- --                                                                               -- -- --                                     HCF.sub.2 CF.sub.2 O                                                                     B    9   9   0  9  0/R                                                                               --                                                                               9  0  --                                     CF.sub.3 O                                                                               B    9   9   4  -- -- --                                                                               7  -- --                                     HCF.sub.2 O                                                                              B    9   6   0  0  -- --                                                                               0  -- --                                     HCF.sub.2 O                                                                              S    9   8   0  0  -- --                                                                               0  -- --                                     HCCl.sub.2 CF.sub.2 O                                                                    B    9   0   0  -- -- --                                                                               4/R                                                                               -- --                                     HCCL.sub.2 CF.sub.2 O                                                                    S    9   9   7  -- -- --                                                                               5  0/R                                                                               --                                      ##STR45##                                                                               B    9   9   7  -- -- --                                                                               9  0  0                                                             0                                                        ##STR46##                                                                               S    9   9   6  -- -- --                                                                               9/R                                                                               0/R                                                                               0/R                                    HCF.sub.2 CF.sub.2 S                                                                     B    9   9   -- -- -- --                                                                               0/R                                                                               -- --                                     HCF.sub.2 CF.sub.2 S                                                                     S    9   9   6  -- -- --                                                                               0/R                                                                               -- --                                     CF.sub.3 CH.sub.2 O                                                                      B    4   0   -- -- -- --                                                                               0/R                                                                               0  --                                     CF.sub.3 CH.sub.2                                                                        S    9   8   6  -- -- --                                                                               0/R                                                                               0  --                                     HCF.sub.2 S                                                                              B    8   9   -- -- -- --                                                                               0/R                                                                               0/R                                                                               0                                      HCF.sub.2 S                                                                              S    9   9   -- -- -- --                                                                               0/R                                                                               -- --                                     CF.sub.3                                                                          Cl     B    9   9   -- -- -- --                                                                               4/R                                                                               0/R                                                                               0                                      CF.sub.3                                                                          Br     B    9   9   9  -- -- --                                                                               0/R                                                                               -- --                                     CF.sub.3                                                                          Br     S    9   8   0  -- -- --                                                                               0/R                                                                               0/R                                                                               --                                                            9                                                       CF.sub.3                                                                          HCF.sub.2 CF.sub.2 O                                                                  B    9   9   9  -- -- --                                                                               13 -- --                                                            0                                                       Br HCF.sub.2 CF.sub.2 O                                                                  B    9   9   -- -- '  --                                                                               0/R                                                                               -- --                                     Cl HCF.sub.2 CF.sub.2 O                                                                  B    9   9   0  -- -- ' 0/R                                                                               0                                         Cl HCF.sub.2 CF.sub.2 O                                                                  S    9   9   -- -- -- --                                                                               0/R                                                                               -- --                                                    0   0                                                           R.sub.1 R.sub.1 '/R.sub.2 R.sub.2 '                                             ##STR47##                                                                               S    9   8   6  -- -- --                                                                               0/R                                                                               0  --                                      ##STR48##                                                                               S    9   0   4  -- -- --                                                                               0/R                                                                               0/R                                                                               --                                      ##STR49##                                                                               B    9   9   0  -- -- --                                                                               0/R                                                                               0/R                                                                               --                                                        0                                                            ##STR50##                                                                               S    9   0   -- -- -- --                                                                               0/R                                                                               -- --                                     Cl        HNO.sub.3                                                                           9   0   -- -- -- --                                                                               0  -- --                                     Br        HNO.sub.3                                                                           9   5   -- 0  -- --                                                                               -- -- --                                     CF.sub.3  HCl  9   9   0  9  0/R                                                                               0 5  0/R                                                                               --                                     Cl        HCl  8   0/R 0  -- -- --                                                                               0  -- --                                                    9/R                                                             Cl        Base 9   0   0  5  -- --                                                                               0  -- --                                     CF.sub.3 O                                                                               HCl  9   9   0  9  -- --                                                                               -- -- --                                     Cl Br     HCl  9   2/R -- 0  -- --                                                                               0  -- --                                     CF.sub.3                                                                          Br     HCl  9   --  -- 9  0/R                                                                               0 0/R                                                                               0/R                                                                               0                                      __________________________________________________________________________      R* -- Indicates reduced feeding observed                                 

                                      TABLE IC                                     __________________________________________________________________________     Evaluation of diaminoguanidine hydrazones as insecticides                       ##STR51##                                                                     wherein unless specified R.sub.1 ' and R.sub.2 ' are H                                                              Mortality Rating                                                               Southern Tobacco Budworm                                                       Armyworm 1st Instar                                                                             3rd Instar                Compound                            1000                                                                              100                                                                               10 300                                                                               100                                                                               10                                                                               1000                                                                              100                                                                               10                 __________________________________________________________________________     R.sub.1      R.sub.2      R.sub.5                                              CF.sub.3     CF.sub.3     CH.sub.3   9  9  3  -- -- --                                                                               6/R*                                                                              -- --                 HCF.sub.2 CF.sub.2 O                                                                        HCF.sub.2 CF.sub.2 O                                                                        CH.sub.3   9  9  -- -- -- --                                                                               -- -- --                                                         9                                      CF.sub.3     CF.sub.3     C.sub.2 H.sub.5                                                                           9  7  9  -- -- --                                                                               -- -- --                 Cl           Cl           C.sub.2 H.sub.5                                                                           8  9  -- -- -- --                                                                               -- -- --                 HCF.sub.2 O  HCF.sub.2 O  C.sub.2 H.sub.5                                                                           9  9  0  -- -- --                                                                               2  -- --                 CF.sub.3 O   CF.sub.3 O   C.sub.2 H.sub.5                                                                           9  9  6  -- -- --                                                                               7/R                                                                               2  --                 CF.sub.3 and Br                                                                             Br and CF.sub.3                                                                             C.sub.2 H.sub.5                                                                           9  9  0  -- -- --                                                                               0/R                                                                               -- --                 CF.sub.3 and Cl                                                                             Cl and CF.sub.3                                                                             C.sub.2 H.sub.5                                                                           9  9  0  -- -- --                                                                               8  0/R                                                                               --                 HCF.sub.2 S  HCF.sub.2 S  C.sub.2 H.sub.5                                                                           9  0  -- -- -- --                                                                               0/R                                                                               -- --                 HCF.sub.2 S  HCF.sub.2 O   -n-C.sub.3 H.sub.7                                                                       9  0  -- -- -- --                                                                               0  -- --                 CF.sub.3     CF.sub.3      -n-C.sub.3 H.sub.7                                                                       9  9  4  -- -- --                                                                               0  -- --                 CF.sub.3     CF.sub.3      .sub.-i-C.sub.3 H.sub.7                                                                  9  9  9  0  -- --                                                                               3/R                                                                               0/R                                                                               --                 HCF.sub.2 CF.sub.2 O                                                                        HCF.sub.2 CF.sub.2 O                                                                         .sub.-i-C.sub.3 H.sub.7                                                                  9  9  0  -- -- --                                                                               5  0  --                 HCCL.sub.2 CF.sub.2 O                                                                       HCCl.sub.2 CF.sub.2 O                                                                        .sub.-i-C.sub.3 H.sub.7                                                                  7  0  -- -- -- --                                                                               0/R                                                                               0/R                                                                               --                 CF.sub.3 O   CF.sub.3 O    .sub.-i-C.sub.3 H.sub.7                                                                  9  9  7  -- -- --                                                                               5  5/R                                                                               --                                                                       9                         ##STR52##                                                                                   ##STR53##    .sub.-i-C.sub.3 H.sub.7                                                                  9  9  0  -- -- --                                                                               0/R                                                                               -- --                 HCF.sub.2 CF.sub.2 S                                                                        HCF.sub.2 CF.sub.2 S                                                                         .sub.-i-C.sub.3 H.sub.7                                                                  9  9  -- -- -- --                                                                               5/R                                                                               0  --                 R.sub.1 R.sub.1 '/R.sub.2 R.sub.2 '                                                                      R.sub.5                                               ##STR54##                                                                                   ##STR55##    .sub.-i-C.sub.3 H.sub.7                                                                  8  5  0  -- -- --                                                                               0/R                                                                               0  --                 CF.sub.3     CF.sub.3      -n-C.sub.4 H.sub.9                                                                       9  0  -- -- -- --                                                                               0  -- --                 CF.sub.3     CF.sub.3      .sub.-i-C.sub.4 H.sub.9                                                                  9  0  -- 0  -- --                                                                               0  -- --                 R.sub.1      R.sub.2      R.sub.5                                              CF.sub.3     CF.sub.3                                                                                     ##STR56## 9  9  6  -- -- --                                                                               6/R                                                                               0/R                                                                               --                 CF.sub.3 O   CF.sub.3 O                                                                                   ##STR57## 9  9  0  -- -- --                                                                               8  0/R                                                                               --                 Cl           Cl                                                                                           ##STR58## 9  0  -- -- -- --                                                                               0/R                                                                               0  --                 CF.sub.3     CF.sub.3     ClCH.sub.2 CH.sub.2                                                                       9  9  8  -- -- --                                                                               2/R                                                                               0  --                 CF.sub.3 O   CF.sub.3 O   ClCH.sub.2 CH.sub.2                                                                       9  9  5  -- -- --                                                                               8/R                                                                               0/R                                                                               0/R                HCF.sub.2 CF.sub.2 O and Cl                                                                 Cl and HCF.sub.3 CF.sub.2 O                                                                 ClCH.sub.2 CH.sub.2                                                                       9  9  -- -- -- --                                                                               0/R                                                                               -- --                  ##STR59##                                                                                   ##STR60##   ClCH.sub.2 CH.sub.2                                                                       9  9  -- -- -- --                                                                               0/R                                                                               -- --                 HCF.sub.2 CF.sub.2 O and CF.sub.3 O                                                         CF.sub.3 O and HCF.sub.2 CF.sub.2 O                                                         ClCH.sub.2CH.sub.2                                                                        9  9  -- -- -- --                                                                               0/R                                                                               -- --                 HCF.sub.2 S  HCF.sub.2 S  ClCH.sub.2 CH.sub.2                                                                       9  0  -- -- -- --                                                                               0/R                                                                               -- --                 CF.sub.3     CF.sub.3     BrCH.sub.2 CH.sub.2                                                                       9  0  0  -- -- --                                                                               0  -- --                 CF.sub.3     CF.sub.3     Cl.sub.3 CCH.sub.2                                                                        9  9  8  -- -- --                                                                               8  0/R                                                                               0                  CF.sub.3 O   CF.sub.3 O   Cl.sub.3 CCH.sub.2                                                                        9  9  9  -- -- --                                                                               0/R                                                                               1/R                                                                               --                 CF.sub.3     CF.sub.3     Cl.sub.3 CC(CH.sub.3).sub.2                                                               9  9  0  -- -- --                                                                               9  0/R                                                                               0                  CF.sub.3     CF.sub.3     CH.sub.2CHCH.sub.2                                                                        9  9  0  -- -- --                                                                               0/R                                                                               0  --                 CF.sub.3 O   CF.sub.3 O   CH.sub.2CHCH.sub.2                                                                        9  8  6  -- -- --                                                                               0/R                                                                               -- --                 CF.sub.3     CF.sub.3                                                                                     ##STR61## 9  0  -- 0  -- --                                                                               0  -- --                 __________________________________________________________________________      R*  indicates reduced feeling is observed                                 

What is claimed is:
 1. A method for the preparation compounds of the formula ##STR62## wherein R₁ ' is H, and R₁ is fluoro, chloro, bromo, trifluoromethyl, CF₃ CH₂ O, CHF₂ X, CF₃ X, CHY₂ --CF₂ X, or CHFYCF₂ X, where X is O or S and Y is F or Cl; R₁ and R₁ ' are --OCF₂ O--, OC(CH₃)₂ --O--, OCF₂ CHFO-- or --OCF₂ CF₂ O--; comprising, reacting a symetrical compound of the formula ##STR63## wherein R₁ and R₁ ' are as described above with a minimum of one molar equivalent of hydroxylamine hydrochloride dissolved in an alcoholic solvent and admixing at from 20° C. to reflux for from 0.5 to 8 hours.
 2. A method for the preparation of unsymetrical diaminoguanidine compounds of the formula ##STR64## wherein R₁ ' and R₂ ' are H, and R₁ and R₂ are individually selected from fluoro, chloro, bromo, trifluoromethyl, CF₃ CH₂ O, CHF₂ X, CF₃ X, CHY₂ CF₂ X, or CHFYCF₂ X, where X is O or S and Y is F or Cl; or wherein R₁ and R₁ ' or R₂ and R₂ ' are --OCF₂ O--, OC(CH₃)₂ --O--, OCF₂ CHFO-- or --OCF₂ CF₂ O--; comprising, reacting a symetrical compound of the formula ##STR65## wherein R₁ and R₁ ' are as described above with a minimum of one molar equivalent of hydroxylamine hydrochloride in an alcoholic solvent, whereby the monosubstituted guanidine of the formula ##STR66## is formed, and reacting the thus-formed monosubstituted guanidine of the formula ##STR67## with an aldehyde of the formula ##STR68## wherein R₂ and R₂ ' are as described above.
 3. The method according to claim 1, wherein the alcoholic solvent is ethanol.
 4. The method according to claim 2, wherein the alcoholic solvent is ethanol. 